EP1883986A2 - Electrolyte matrix for molten carbonate fuel cells with improved pore size and method of manufacturing same - Google Patents
Electrolyte matrix for molten carbonate fuel cells with improved pore size and method of manufacturing sameInfo
- Publication number
- EP1883986A2 EP1883986A2 EP06759482A EP06759482A EP1883986A2 EP 1883986 A2 EP1883986 A2 EP 1883986A2 EP 06759482 A EP06759482 A EP 06759482A EP 06759482 A EP06759482 A EP 06759482A EP 1883986 A2 EP1883986 A2 EP 1883986A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- matrix
- accordance
- milling
- making
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
- H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0295—Matrices for immobilising electrolyte melts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/144—Fuel cells with fused electrolytes characterised by the electrolyte material
- H01M8/145—Fuel cells with fused electrolytes characterised by the electrolyte material comprising carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- a fuel cell is a device which directly converts chemical energy stored in hydrocarbon fuel into electrical energy by means of an electrochemical reaction.
- a fuel cell comprises an anode and a cathode separated by an electrolyte, which serves to conduct electrically charged ions.
- an electrolyte which serves to conduct electrically charged ions.
- a number of individual fuel cells are stacked in series with an electrically conductive separator plate between each cell.
- MCFCs Molten carbonate fuel cells
- the anode and the cathode of MCFCs are isolated from one another by a porous electrolyte matrix which is saturated with carbonate electrolyte.
- the matrix typically comprises a porous, unsintered ⁇ -LiAlCh ceramic powder bed impregnated with molten alkali carbonate electrolyte and provides ionic conduction and gas sealing.
- the matrix experiences both mechanical and thermal stresses which contribute to cracking or defects in the matrix.
- the electrolyte matrix In order to provide effective gas sealing, the electrolyte matrix must have sufficient strength, mechanical integrity and materials endurance to withstand these stresses, particularly during thermal cycles of the MCFC.
- the matrix must be able to accommodate volume changes associated with carbonate melting and solidification during MCFC thermal cycling, to provide resistance to pressure differences across the matrix and to wet seal holding pressure over long periods of time, and must have slow or no pore growth over MCFC lifetime.
- the matrix must have sufficient porosity and sub-micron pore distribution to ensure strong capillary forces so as to effectively retain electrolyte within its pores to prevent flooding of the electrodes and the drying out of the matrix. Accordingly, various methods for strengthening the electrolyte matrix and for improving its electrolyte retention have been developed. For example, U.S.
- Patent No. 4,322,482 discloses use of "crack attenuator" particles having a larger size in the matrix to reduce through-cracking of the matrix.
- Another method of manufacturing an electrolyte matrix having increased strength and improved uniformity is disclosed in U.S. Patent No. 5,869,203, assigned to the same assignee herein.
- the '203 patent discloses a method of fabricating the electrolyte matrix comprising ceramic support material and an additive material employing a high-energy intensive milling technique of the support and additive materials to produce highly active particles of smaller size.
- the high-energy milling technique of the '203 patent is carried out by adding the additive material to a slurry of the support material and milling the slurry mixture such that the particle size of the additive is less than 0.5 ⁇ m.
- the matrix is then formed from the slurry mixture by a tape casting technique.
- the high-energy milling technique of the '203 patent has been effective in increasing the strength and uniformity of the electrolyte matrix.
- particle packing and pore structure of the matrix fabricated using the conventional methods, including the method disclosed in the '203 patent are significantly affected by the environmental conditions, and particularly by humidity, and the process conditions during the tape casting process as well as by variations in the raw matrix materials.
- a method of making a matrix element for carrying a carbonate electrolyte comprising providing a carbonate electrolyte material, pre- milling the carbonate electrolyte material to form a pre-milled carbonate electrolyte having a particle size of less than 0.3 microns, providing a support material, mixing the pre-milled carbonate electrolyte with the support material using a milling technique to form a mixture, and forming the mixture into the matrix element.
- the step of providing the carbonate electrolyte also includes dispersing the electrolyte in a predetermined amount of dispersant and the pre-milling is carried out with the carbonate electrolyte dispersed in the dispersant such as fish oil or one or more of Hypermer KD-series polymeric dispersants.
- the predetermined amount of dispersant is equal to 1 to 5% of carbonate electrolyte weight.
- the support material is LiAlO 2 and the carbonate electrolyte material is one or more OfLi 2 CO 3 , K 2 CO 3 and Na 2 CO 3 .
- the method may further comprise providing one or more additive components to the mixture of pre-milled carbonate electrolyte and support material, wherein the additive components include at least one of a binder and a plasticizer.
- Acryloid binder and Santicizer® plasticizer may be used as the additive components.
- the forming of the matrix element is carried out by casting the mixture and then drying the casted mixture to form a tape element, and may further include heating the tape element to remove the dispersant from the tape element.
- a fuel cell comprising an electrolyte matrix prepared according to this method is also disclosed.
- FIG. 1 shows a molten carbonate fuel cell using an electrolyte matrix in accordance with the principles of the present invention
- FIG. 2 shows a flow diagram of a method of fabricating the electrolyte matrix of FIG. 1 in accord with the invention
- FIG. 3 shows a graph of pore size distribution data of electrolyte matrix samples fabricated using the method of FIG. 2 and of electrolyte matrix tapes prepared using a conventional method
- FIG, 4 shows a bar graph of the bending strengths of electrolyte matrix samples formed from different types of LiAlO 2 powder prepared with and without pre-milling of electrolyte;
- FIG. 5 shows a graph of pore size distributions of electrolyte matrix samples formed using the method of FIG. 2 from LiAlO 2 having different purity levels
- FIG. 6 shows a graph of pore size distribution data of electrolyte matrix samples tested at different humidity levels
- FIG. 7 shows a graph of projected MCFC lifetime for conventional MCFCs and for MCFCs using an electrolyte matrix prepared using the method of FIG. 2.
- FIG. 1 shows a molten carbonate fuel cell 1 including an electrolyte matrix 2 fabricated in accordance with the principles of the present invention.
- the fuel cell 1 also includes an anode 3 and a cathode 4 which are separated from one another by the matrix 2.
- Fuel gas is fed to the anode 3 and oxidant gas is fed to the cathode 4.
- these gases undergo an electrochemical reaction in the presence of molten carbonate electrolyte present in the pores of the electrolyte matrix 2.
- the matrix 2 comprises a support material, one or more additive components and carbonate electrolyte.
- the support material comprises a porous ceramic material having a sub-micron particle size.
- LiAlO 2 including ⁇ - LiAlO 2 , (X-LiAlO 2 and ⁇ -LiA10 2 , are used as the support material.
- the additive components may include binder, plasticizer and other suitable materials.
- the electrolyte is disposed in the pores of the support material and comprises an alkali carbonate, such as Li 2 CO 3 , K 2 CO 3 or Na 2 CO 3 . It is understood that other materials may be suitable for use in the electrolyte matrix 2 of the fuel cell.
- FIG. 2 shows a flow diagram of a method for fabricating the matrix 2 of FIG. 1 in accord with the principles of the present invention.
- the carbonate electrolyte is pre-milled so that the mean particle size of the resulting pre-milled electrolyte is equal to or is smaller than the mean particle size of the ceramic support material.
- the total surface area of the carbonate electrolyte particles will be equal to or greater than the total surface area of the support material particles.
- the desired mean particle size of the carbonate electrolyte should be less than 0.3 microns.
- any conventional milling method may be employed for pre-milling the carbonate electrolyte, including, but not limited to attrition milling and ball milling.
- the pre-milling conditions such as the grinding media materials, size and loading of the grinding media and the grinding speed can be optimized to achieve a desired mean particle size of the pre-milled electrolyte, as well as a desired particle size distribution.
- the pre-milling of the carbonate electrolyte may be accomplished in the presence of a dispersant.
- the dispersant is used to disperse the electrolyte so as to prevent re-agglomeration of electrolyte particles.
- Dispersants such as fish oil and one or more of Hypermer KD-series polymeric dispersants are suitable for dispersing electrolyte during the pre-milling process.
- the amount of dispersant used may be varied based on the targeted surface area of the pre-milled electrolyte.
- the pre-milled electrolyte is mixed with the support material, which will form the body of the prepared electrolyte matrix 2 shown in FIG. 1.
- the support material typically comprises a ceramic material such as, for example, LiAlO 2 .
- the mixture prepared in the second step S 102 is milled for a predetermined period of time to break down any agglomerates present in the mixture and to form a slurry having the support material particles and the electrolyte particles uniformly dispersed throughout the slurry.
- the milling of the mixture can be accomplished using any conventional milling process, such as attrition milling, ball milling or fluid energy grinding.
- organic additives may be added to the slurry prepared in step S 103 to prevent cracking of the matrix 2 prepared using this method.
- the cracking of the matrix may occur when the matrix is used in a fuel cell during operation as a result of the increased overall surface area of the matrix.
- additives may include a binder and a plasticizer.
- acryloid binder and plasticizer for example, acryloid binder and
- Santicizer® 160 plasticizer are suitable for use as the organic components to be added to the slurry.
- the amount of organic additives added to the slurry may comprise approximately 10 to 30 % by weight of all solid components, i.e. electrolyte, support material and additives, of the slurry.
- the slurry mixed with organic additives in the fourth step S 104 is formed into one or more electrolyte matrix elements in a fifth step S 105 of the matrix fabrication method.
- the electrolyte matrix elements may be formed by any suitable conventional technique. Tape casting is a preferred technique for forming the matrix element in which the slurry is tape cast using a doctor blade and then dried.
- the dry tape cast slurry results in a flat and flexible green tape having nearly theoretical as-cast green density and nearly 0% green porosity.
- the green tape then undergoes a burnout procedure during which the tape is heated to a predetermined temperature for a predetermined period of time to remove the dispersant by combustion and to produce a completed electrolyte matrix element.
- a plurality of green tapes may be prepared from the slurry to form multiple completed matrix elements.
- the completed matrix element comprises the ceramic matrix 2 formed from the support material with the carbonate electrolyte particles dispersed in the matrix.
- the carbonate electrolyte particles define the pore sizes in the matrix.
- Example 1 An illustrative example of fabricating an electrolyte matrix is described herein below.
- Example 1 An illustrative example of fabricating an electrolyte matrix is described herein below.
- LiAlO 2 is used as the support material in the matrix and Li 2 CO 3 is the electrolyte material.
- the method shown in FIG. 2 and described above is used to fabricate matrix elements filled with electrolyte in accord with the invention.
- Li 2 CO 3 is pre-milled to a mean particle size of less than 0.3 microns, and preferably 0.1 to 0.2 microns. Since a typical surface area Of LiAlO 2 particles is 10 m 2 /g, the desired surface area of pre-milled Li 2 CO 3 particles is about 10 m 2 /g.
- the Li 2 CO 3 is pre-milled in the presence of a fish oil dispersant to prevent re-agglomeration of the Li 2 CO 3 particles after the pre- milling step.
- the amount offish oil used in this step is equal to approximately 1 to 5% of the weight OfLi 2 CO 3 .
- an attrition milling technique using YTZ® grinding media having 2 to 6 mm ball size is employed to pre-mill Li 2 CO 3 to the particle size between 0.1 and 0.2 microns.
- the grinding media loading is between 60 and 80%, and preferably about 70%, and the grinding speed is between 2,000 and 3,000 rpm.
- step S 102 the pre-milled Li 2 CO 3 is mixed with the support material LiAlO 2 and in the third step S 103, the resulting mixture is milled for approximately 2 hours to form a slurry.
- step S 103 the attrition milling technique is employed. During this step, any agglomerates present in the mixture are broken down and the Li 2 CO 3 and LiAlO 2 particles are uniformly dispersed throughout the slurry.
- additives including a binder and a plasticizer
- acryloid binder and Santicizer® 160 plasticizer are used as the additives.
- the amount of these additives added to the slurry in this example is approximately 21% by weight of all solid components, i.e. Li 2 CO 3 , LiAlO 2 and additives, of the slurry.
- the mixture of the slurry and the additives is then formed into electrolyte matrix elements using the tape casting technique.
- the slurry is tape cast using a doctor blade and dried at about 60° Celsius for 0.5 hours, to form a plurality of green tapes. These tapes are then heated to a temperature of about 400° Celsius for approximately 2 hours to remove the fish oil dispersant by combustion and to produce completed electrolyte matrix elements.
- the electrolyte matrix elements fabricated using the above method have improved particle packing, unique narrow pore size distribution and significantly improved mechanical strength.
- the pore structure of these electrolyte matrix elements is more refined, having smaller mean pore size and narrower pore size distribution as compared with conventional electrolyte matrix.
- the smaller mean pore size and narrower pore size distribution contribute to the improved strength and endurance of the matrix during MCFC thermal cycling and to greater electrolyte retention by the matrix.
- FIG. 3 shows a graph of pore size distribution data for electrolyte matrix tapes fabricated using the method of FIG. 2 and for conventional electrolyte matrix tapes prepared using the method described in the '203 patent.
- the matrix tapes prepared using either of these methods were formed from the same components.
- LiAlO 2 was used as the support material for the matrix tapes and Li 2 CO 3 was used as the electrolyte.
- the X-axis represents the pore size of the matrix in microns, while the Y-axis represents a log differential for the cumulative pore volume in mL/g.
- the conventional matrix tapes had a broad dual-peak pore size distribution with pores ranging between 0.04 and 0.6 microns in size.
- the conventional tapes had a frequent occurrence of larger pores having a pore size of about 0.5 microns as well as a large number of smaller pores having a pore size of about 0.14 microns.
- the matrix tapes fabricated using the method of FIG. 2 employing pre-milling of Li 2 CO 3 had a significantly narrower single-peak pore size distribution with pores ranging between 0.04 microns and 0.3 microns in size.
- the peak number of pores in these matrix tapes had a pore size of about 0.14 microns.
- the pre-milling OfLi 2 CO 3 during fabrication of the electrolyte matrix resulted in the matrix having a smaller and more uniform pore size.
- the majority of larger pores with a pore size of about 0.5 microns were eliminated from the matrix.
- FIG. 4 shows a bar graph of the bending strengths of matrix tapes formed from different types Of LiAlO 2 powder which were prepared with or without the pre- milling OfLi 2 CO 3 .
- the bending strengths of the conventional electrolyte matrix samples formed with CC-LiAlO 2 having 94% purity, 0.15 micron primary particle size and 10 m 2 /g surface area (Powder A) and Ot-LiAlO 2 having 96% purity, 0.11 micron primary particle size and 11 m 2 /g surface area (Powder B) were approximately 380 psi and 400 psi, respectively.
- the bending strength of an electrolyte matrix sample prepared using the method of FIG. 2 with Powder A was about 625 psi
- the bending strength of a sample prepared using the method of FIG. 2 with Powder B was about 680 psi
- FIG. 5 shows a graph of pore size distribution data for the electrolyte matrix samples tested.
- the X-axis represents the pore size in microns, while the Y-axis represents a relative frequency of occurrence.
- the electrolyte matrix samples prepared with Powder A had a pore size distribution between 0.08 and 0.5 microns, with the most frequently occurring pores being in the pore size range between 0.1 and 0.3 microns.
- the electrolyte matrix samples prepared with Powder B or Powder C had a pore size distribution between 0.05 and 0.2 microns.
- the majority of the pores in the sample prepared with Powder B had a pore size of approximately 0.1 microns.
- the most frequently occurring pore sizes were between 0.07 and 0.2.
- the pre-milling OfLi 2 CO 3 during the fabrication of the samples eliminated the dual-peak pore size distribution, regardless of the purity of the LiAlO 2 support material and resulted in a narrower, and thus more uniform, pore size distribution in each of the samples.
- FIG. 6 shows a graph of pore size distribution data of the electrolyte matrix samples 601-604 formed at these humidity levels.
- the samples 601, 602 and 603 were each formed with LiAlO 2 powder having 94% purity (Powder A) using the tape casting technique at 27% relative humidity, while sample 604 was formed with Powder A by tape casting at 57% relative humidity.
- the pore size distribution of each of the samples 601-604 was between 0.03 and 0.3 with the peak number of pores having a size of approximately 0.19 microns.
- the humidity during the tape casting process was increased from 27% to 57%, the pore size distribution of the completed matrix elements remained about the same as the pore size distribution of the samples formed at 27% humidity. Accordingly, it can be seen that the environmental humidity during the tape casting process has little or no effect on the pore size distribution, and thus on the mechanical integrity and electrolyte retention characteristics, of the completed electrolyte matrix samples fabricated using the method of FIG. 2.
- the lifetime of the MCFC is affected by a variety of factors including loss of electrolyte, the drying out of the matrix, the strength of the matrix and its gas sealing capacity.
- pores having a size greater than 0.3 microns in conventional electrolyte matrices contribute to a loss of approximately 30% of the electrolyte stored in the matrix.
- smaller pores and more uniform porosity of the matrix fabricated in accordance with the present invention significantly reduce the loss of electrolyte from the matrix, preventing the drying out of the matrix and a possible cross-over of the fuel and oxidant gases.
- the improved strength and characteristics of the electrolyte matrix prepared as shown in FIG. 2 significantly reduce the risk of cracking of the matrix. Therefore, the improvements in the electrolyte matrix fabricated in accord with the invention increase the operating life of MCFCs.
- FIG. 7 shows a graph of projected MCFC lifetime for single-cell MCFCs and MCFC stacks using conventional electrolyte matrices and for single-cell MCFCs and stacks using electrolyte matrices prepared using the method of FIG. 2.
- the X-axis represents the lifetime of the fuel cell in hours, while the Y-axis represents the actual electrolyte fill level of the fuel cells.
- the lifetimes of MCFCs and stacks were determined based on the fill level of the Li 2 CO 3 electrolyte in the cells, with a minimum electrolyte fill level required for MCFC operation being about 75%.
- the minimum electrolyte fill level was reached after about 3,500 hours of operation, this operating time representing a projected lifetime of conventional single-cell MCFCs.
- the projected lifetime of single-cell MCFCs 702 which employed electrolyte matrices fabricated using the method of FIG. 2 was increased to about 6,900 hours due to the improved electrolyte retention of these cells.
- a similar increase in a projected lifetime can be seen for MCFC stacks.
- the lifetime of conventional MCFC stacks 703 is approximately 14,000 hours, while the lifetime of MCFC stacks 704 with the matrices prepared using pre-milling of the electrolyte is about 28,000 hours.
- the improved electrolyte retention by electrolyte matrices fabricated in accord with the invention results in nearly doubling the operating life of the MCFC cells and stacks.
- the improvements in the strength of the matrix and the reduced risk of matrix cracking also contribute to extending the lifetime of MCFCs.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/128,909 US20060257721A1 (en) | 2005-05-13 | 2005-05-13 | Electrolyte matrix for molten carbonate fuel cells with improved pore size and method of manufacturing same |
| PCT/US2006/018066 WO2006124449A2 (en) | 2005-05-13 | 2006-05-10 | Electrolyte matrix for molten carbonate fuel cells and method of making |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1883986A2 true EP1883986A2 (en) | 2008-02-06 |
| EP1883986A4 EP1883986A4 (en) | 2009-06-24 |
| EP1883986B1 EP1883986B1 (en) | 2011-09-21 |
Family
ID=37419497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06759482A Ceased EP1883986B1 (en) | 2005-05-13 | 2006-05-10 | Electrolyte matrix for molten carbonate fuel cells with improved pore size and method of manufacturing same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20060257721A1 (en) |
| EP (1) | EP1883986B1 (en) |
| JP (1) | JP2008541385A (en) |
| KR (1) | KR101320195B1 (en) |
| CN (1) | CN101443942A (en) |
| WO (1) | WO2006124449A2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5308388B2 (en) | 2010-03-31 | 2013-10-09 | 三菱重工業株式会社 | Gear processing machine |
| KR101146944B1 (en) | 2010-04-14 | 2012-05-22 | 두산중공업 주식회사 | Fabrication Method of Electrolyte impregnanted Cathodes |
| US9225030B1 (en) * | 2011-06-20 | 2015-12-29 | University Of South Carolina | Mixed proton and carbonate ion conductor |
| US20150214564A1 (en) * | 2014-01-27 | 2015-07-30 | Fuelcell Energy, Inc. | Fuel cell matrix composition and method of manufacturing same |
| KR101795894B1 (en) * | 2015-12-24 | 2017-12-01 | 주식회사 포스코 | Gasket for molten carbonate fuel cell having a oxide barrier layer for the prevention of electrolyte migration |
| CN110911717B (en) * | 2019-12-03 | 2021-03-23 | 中国华能集团清洁能源技术研究院有限公司 | Electrolyte supplementing method for molten carbonate fuel cell stack |
| CN112928318A (en) * | 2021-03-18 | 2021-06-08 | 华能国际电力股份有限公司 | Binderless molten carbonate fuel cell electrolyte membrane and preparation method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115632A (en) * | 1977-05-05 | 1978-09-19 | The United States Of America As Represented By The United States Department Of Energy | Method of preparing electrolyte for use in fuel cells |
| US4322482A (en) * | 1980-06-09 | 1982-03-30 | United Technologies Corporation | Electrolyte matrix for molten carbonate fuel cells |
| US4540640A (en) * | 1983-04-29 | 1985-09-10 | The United States Of America As Represented By The United States Department Of Energy | Coated powder for electrolyte matrix for carbonate fuel cell |
| US4526812A (en) * | 1983-04-29 | 1985-07-02 | The United States Of America As Represented By The United States Department Of Energy | Coated powder for electrolyte matrix for carbonate fuel cell |
| EP0509424A2 (en) * | 1991-04-16 | 1992-10-21 | Institute of Gas Technology | Composite active electrolyte-matrix and laminated component tapes for molten carbonate fuel cells |
| US5399443A (en) * | 1992-02-12 | 1995-03-21 | Electric Power Research Institute, Inc. | Fuel cells |
| JP3350167B2 (en) * | 1993-09-03 | 2002-11-25 | 株式会社東芝 | Molten carbonate fuel cell |
| US5478663A (en) * | 1994-03-22 | 1995-12-26 | International Fuel Cells Corporation | Edge seals for molten carbonate fuel cell stacks |
| US5869203A (en) * | 1996-12-13 | 1999-02-09 | Energy Research Corporation | Electrolyte matrix for molten carbonate fuel cells |
| US6010085A (en) * | 1999-03-17 | 2000-01-04 | Kerr Corporation | Agitator mill and method of use for low contamination grinding |
| US6544467B2 (en) * | 2000-12-18 | 2003-04-08 | Delphi Technologies, Inc. | Exhaust gas sensor and the method of manufacture thereof |
| US6884269B2 (en) * | 2002-06-13 | 2005-04-26 | Fuelcell Energy, Inc. | Continuous method for manufacture of uniform size flake or powder |
-
2005
- 2005-05-13 US US11/128,909 patent/US20060257721A1/en not_active Abandoned
-
2006
- 2006-05-10 KR KR1020077029052A patent/KR101320195B1/en not_active Expired - Fee Related
- 2006-05-10 WO PCT/US2006/018066 patent/WO2006124449A2/en not_active Ceased
- 2006-05-10 EP EP06759482A patent/EP1883986B1/en not_active Ceased
- 2006-05-10 JP JP2008511313A patent/JP2008541385A/en not_active Withdrawn
- 2006-05-10 CN CNA200680013672XA patent/CN101443942A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006124449A2 (en) | 2006-11-23 |
| WO2006124449A3 (en) | 2008-08-28 |
| EP1883986B1 (en) | 2011-09-21 |
| JP2008541385A (en) | 2008-11-20 |
| KR20080011694A (en) | 2008-02-05 |
| CN101443942A (en) | 2009-05-27 |
| EP1883986A4 (en) | 2009-06-24 |
| KR101320195B1 (en) | 2013-10-30 |
| US20060257721A1 (en) | 2006-11-16 |
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